Chemical Engineering & Processing: Process Intensification 117 (2017) 80–88

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Chemical Engineering & Processing: Process Intensification

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Full-length article

Design and optimization of dimethyl ether production from crude glycerol in MARK
a reactive distillation
⁎
Punjawat Kaewwisetkula, Lida Simasatitkulb, Amornchai Arpornwichanopa,
a
Computational Process Engineering Research Unit, Department of Chemical Engineering, Faculty of Engineering, Chulalongkorn University, Bangkok 10330, Thailand
b
Department of Industrial Chemistry, Faculty of Applied Science, King Mongkut’s University Technology of North Bangkok, Bangkok 10800, Thailand

A R T I C L E I N F O A B S T R A C T

Keywords: Methanol in crude glycerol from biodiesel production is considered to be a raw material for dimethyl ether
Reactive distillation production. In this work, the production of dimethyl ether from the dehydration reaction of methanol in a
Crude glycerol reactive distillation is studied. A model of the reactive distillation is developed using a process simulator and
Dimethyl ether used to analyze its performance by considering both the methanol conversion and the total annual cost. The
Design
effect of key operating parameters on conversion of methanol is reported. The optimal process design is
Optimization
determined in terms of the minimization of total annual cost.

1. Introduction
Today, many countries are facing a major problem in the growing
fuel crisis. This crisis is primarily attributed to the increasing energy
demand from the growing population and the limited reserves of
conventional fossil fuels. For this reason, searching for environmentally
friendly alternative fuels has become an important issue. Among the
various renewable fuels, biodiesel has received considerable attention,
as it is clean and can be produced from vegetable oils [1].
Generally, a transesterification reaction is most commonly used to
produce biodiesel from alcohol and vegetable oils such as rapeseed oil
and soybean oil, or animal fats. It is known that in this process for the
production of biodiesel, 10% by weight of the vegetable oils or animal
fats are converted to crude glycerol. As a result of the large demand for
biodiesel in many countries, a large amount of crude glycerol is
generated. However, the crude glycerol contains many impurities such
as methanol, the remaining catalyst, water, soap, salt and esters, which
are generated during the reaction step [2,3]. The composition of crude
glycerol generally depends on the specific biodiesel production process,
the type of catalyst, raw materials used (i.e., the type of vegetable oil)
and the level of post-treatments for each biodiesel production process.
Crude glycerol and refined crude glycerol are processed through
filtration, chemical addition and fractional vacuum distillation before
sending to suppliers. Due to the high specific heat capacity of glycerol, a
high energy consumption is required for vaporization. Hence, a
distillation column is suitable for the purification of crude glycerol.
The pharmaceutical, cosmetic and food industries require a higher
purity grade of glycerol for which the purification process is more
complex with a higher production cost [2]. However, the market prices
of crude glycerol have been gradually decreasing because of the
oversupply of glycerol caused by the increasing biodiesel production.
For this reason, the use of crude glycerol to produce high value-added
products would reduce the biodiesel production cost and increase the
competitive potential of biodiesel producers [4].
Most industrial biodiesel processes utilize a high molar ratio of
methanol to vegetable oils to force the reactions toward completion.
For this reason, crude glycerol from biodiesel production contains a
large amount of methanol [3]. This mixture of methanol and crude
glycerol is considered to be a valuable reactant to produce other value-
added products, such as dimethyl ether, which is widely used as a
promising alternative fuel to replace conventional diesel and liquefied
petroleum gas (LPG). The benefits of using dimethyl ether instead of
conventional diesel are more complete combustion, lower carbon
monoxide emission, lower nitrogen oxides emission, higher thermal
efficiency, near-zero aromatic emission and zero sulfur emission [5].
For this reason, dimethyl ether is widely used as an alternative fuel for
diesel engines in many countries to meet their stringent emission
regulations (such as EURO 5, US 2010, 2009 Japan). Moreover, the
characteristics of dimethyl ether are similar to those of liquefied
petroleum gas (LPG) but the combustion of dimethyl ether is cleaner
than that of liquefied petroleum gas. Therefore, dimethyl ether can be
used instead of liquefied petroleum gas. Dimethyl ether can be
produced from synthesis gas which is, in turn, produced from many
sources, such as renewable materials (biomass, waste and agricultural
products) and fossil fuels (natural gas and coal). Dimethyl ether is lower
in price than conventional diesel fuel and liquefied petroleum gas.

⁎
Corresponding author.
E-mail address: Amornchai.A@chula.ac.th (A. Arpornwichanop).

http://dx.doi.org/10.1016/j.cep.2017.03.019
Received 15 January 2017; Accepted 29 March 2017
Available online 31 March 2017
0255-2701/ © 2017 Elsevier B.V. All rights reserved.
P. Kaewwisetkul et al. Chemical Engineering & Processing: Process Intensification 117 (2017) 80–88

specifications and calculator block. Two configurations for reactive

Nomenclature
distillation were proposed to improve the purity of the dimethyl ether
product. Both configuration can be considered as a candidate process to
A Arrhenius pre—exponential factor (m3 kg-cat−1 s−1)
compare to conventional process in term of energy saving [13]. It is
k Rate constant of reaction (m3 kg-cat−1 s−1)
noted that the reactive distillation was operated at 10 bar because the
r Reaction rate (mol s−1 kg-cat−1)
reaction rate was promoted at high pressure operation. A reactive
T Temperature (K)
dividing wall columns for the synthesis of dimethyl ether was con-
TAC Total annual cost ($)
firmed to be the configuration that performed better than reactive
distillation in a conventional column [14]. Tavan and Hosseini [15]
also demonstrated that the reactive distillation process for dimethyl
Presently, various commercial projects are actively being developed by
ether production can reduce the operating cost significantly while
major industries especially in Asia and European Union [6]. A mixture
producing dimethyl ether of 99.9% purity. This means that the reactive
of dimethyl ether and liquefied petroleum gas is used as a fuel in China.
distillation process can be done on an industrial scale. Tong et al. [16]
Moreover, the demand for dimethyl ether in China has increased
studied methyl acetate hydrolysis coupled with methanol dehydration
because of the popularization of civil use of LPG and the development
using reactive distillation. The effects of such parameters as feed
of alternatively fueled vehicles. The annual consumption of dimethyl
location and reflux ratio were studied in terms of methanol conversion,
ether shows a stable increasing trend. It can be predicted that the
methyl acetate conversion and dimethyl ether mole fraction. In
annual demand for dimethyl ether will continue to increase dramati-
previous work, reactive distillation was designed for the etherification
cally in the future with the development of dimethyl ether vehicles [5].
of glycerol in terms of the minimization of total annual cost. Pure
Generally, dimethyl ether is produced from the dehydration reac-
glycerol from biodiesel production was used as the raw material
tion of methanol [6]. A batch reactor using various catalysts was firstly
although the purification process for crude glycerol required the use
proposed. Neither complete conversion nor a high purity of dimethyl
of distillation trains [17].
ether was obtained at a high reaction temperature [7]. Tavan et al. [8]
The purpose of this study is to design a reactive distillation for
offered a kinetic constant for the dehydration of methanol and found
dimethyl ether production from the dehydration reaction of methanol
that conversion of methanol is limited to 80% conversion in a fixed bed
in crude glycerol. The total annual cost will be used as the criterion to
reactor. Ghavipour and Behbahani [9] proposed a fixed bed reactor that
determine a suitable design for reactive distillation. The simulation
improved the equilibrium constant and thus increased the conversion to
studies of the reactive distillation are performed using Aspen Plus
83% of an inlet temperature of 593 K. Furthermore, a hot spot existed
simulator. The effects of operating parameters for reactive distillation,
within the reactor because the dehydration reaction of methanol to
such as the number of reactive, rectifying and stripping stages, molar
dimethyl ether is an exothermic reaction [10]. Therefore, reactive
reflux ratio and reboiler duty, on the conversion of methanol in crude
distillation is regarded as a potential alternative as it offers some
glycerol are analyzed. The optimal process design is determined in
advantages over a conventional process especially using the benefit of
terms of the minimization of total annual cost.
the heat from this exothermic reaction [11]. Both the reaction and
separation tasks can be performed in a single unit; therefore, capital
2. Kinetic model of dehydration reaction of methanol into
and operating costs can be reduced. Reactive distillation provides high
dimethyl ether
conversion, improves the yield of products, and reduces energy
consumption [12]. However, a reactive distillation column is hardly
The reaction for the dehydration of methanol is shown in Eq. (1).
ever designed with various design variables, such as the numbers of
The kinetic rate constant for the dehydration reaction of methanol to
rectifying stages, reactive stages, and stripping stages. For this reason,
dimethyl ether is required to perform a process simulation. This work
the use of process flowsheet simulator can facilitate the design process
focuses on the production of dimethyl ether from the dehydration of
of a complicated system like reactive distillation. The simulator has an
methanol. Lei et al. [10] determined a kinetic model for the dehydra-
integrated set of product and process design tools for both synthesis and
tion of methanol to dimethyl ether as shown in Eqs. (2) and (3) by
optimization of the entire innovation and engineering workflow process
fitting the experimental data from a fixed-bed micro-reactor with
throughout the plant. These tools include sensitivity analysis, design
macroporous sulfonic acid ion exchange resin as a catalyst. A list of

Fig. 1. Process flow sheet of dimethyl ether production.

81
P. Kaewwisetkul et al.
the values of the pre-exponential factor and activation energy is given
below.
2CH3OH ↔ CH3OCH3+H2 O (1)
r = k [CH3OH]1.51 [H2 O]−0.51 (2)
⎛ −E ⎞
k = A exp ⎜ a ⎟
⎝ RT ⎠ (3)
where A is the Arrhenius pre-exponential factor
(A = 5.19 × 109 m3 kg-cat−1 s−1) and Ea is the activation energy
(Ea = 133.8 kJ mol−1). The dehydration reaction of methanol to
dimethyl ether using macroporous sulfonic acid ion exchange resin as
a catalyst is an equilibrium reaction and exothermic reaction [10].
Because the production of dimethyl ether is a polar component
system, the NRTL—Redich Kwong model is used to predict the
thermodynamic properties of substances in the system. The interaction
parameters are taken from the Aspen Plus database or estimated using
the UNIFAC-Dortmund modified method.
3. Process flowsheet description
In this work, the design of the reactive distillation column for the
production of dimethyl ether is developed. Methanol in crude glycerol
is used to produce dimethyl ether by reactive distillation. The design
plant flowsheet of this work is presented in Fig. 1. In this plant, the flow
sheet contains two unit operations (reactive distillation and a distilla-
tion column). The pressure drop in both the reactive distillation and
distillation column is negligible. Reactive distillation which can in-
corporate both phase separation and chemical reaction in a single unit
is used to produce dimethyl ether by dehydrating the methanol in crude
glycerol and separates the dimethyl ether from the glycerol and water.
The methanol is completely consumed by the reactive distillation. The
distillation column is used to separate glycerol from water. Firstly, the
feed stream of crude glycerol is sent to a reactive distillation. The
composition of crude glycerol is assumed to consist of 70 mol% glycerol
and 30 mol% methanol. Dimethyl ether, which has a low boiling point,
is separated from the other components at the top of the reactive
distillation column while glycerol and water are sent to the bottom of
the column. Reactive distillation can improve the conversion of
methanol to 99% in order to eliminate a methanol recycle section.
Secondly, glycerol and water from the bottom of the reactive distilla-
tion column are sent into the distillation column in order to separate
glycerol from water. Water is sent to the top of a distillation column as a
waste water stream while pure glycerol is recovered at the bottom of
the distillation column as a glycerol stream.
3.1. Standard conditions for reactive distillation in dimethyl ether
production
The reactive distillation column under standard conditions consists
of 13 stages. The numbering of the stages is from the top downward,
with stage 1 as total condenser and stage n as reboiler. The feed stream
of crude glycerol at a feed flow rate of 3.078 kmol h−1 is sent into
reactive distillation at the first stage of the reactive stages. The reactive
distillation is operated at 8 bar. The reactive stages are stages 5–9. The
standard conditions for reactive distillation are given in Table 1.
All system performances of reactive distillation for dimethyl ether
production were considered in terms of the conversion of methanol.
This was defined in Eq. (4) as follows:
%Conversion
Differenceinmolarflowrateofinletandoutletofmethanol
=
Molarfeedflowrateofmethanolincrudeglyceroltoreactivedistillation
× 100% (4)
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Chemical Engineering & Processing: Process Intensification 117 (2017) 80–88
3.2. Standard conditions of the distillation column
The distillation column under standard conditions consists of 11
stages.
The numbering of the stages is from the top downward, with stage 1
as total condenser and stage n as reboiler. The feed stream of glycerol-
water at a feed flow rate of 2.62 kmol h−1 is sent into the distillation
column operated at 1 bar. The standard conditions for the distillation
column are given at Table 2.
4. Sensitivity analysis
The sensitivity analysis of system performance in terms of conver-
sion is investigated in two parts: a reactive distillation and a distillation,
as shown below.
4.1. Reactive distillation for dimethyl ether production
Fig. 2 shows the effect of reboiler duty on the conversion of
methanol within a range of 20–70 kW. It can be seen that increasing
the reboiler heat duty results in decreasing the conversion of methanol.
As the heat duty increases, the reboiler stream from the reboiler
contains considerable water. This means that water is being recycled
to the reactive stages. Because water inhibits the dehydration of
methanol, conversion of methanol in the reactive stages is decreased
by increasing the reboiler duty.
Fig. 3 shows the effect of feed stage location on the conversion of
methanol. It is found that feeding crude glycerol at the top of the
reactive stages gives the best conversion of methanol. This is due to the
fact that amount of methanol in the reactive stages is decreased when
the feed location of crude glycerol in the reactive distillation is below
the top of the reactive stages. This is because the temperature of the
reactive stages increases from top to bottom. For this reason, when
feeding crude glycerol lower than the top of the reactive stages, liquid
methanol is also converted to the vapor phase. In the case of feeding
crude glycerol above the reactive stages, the conversion of methanol
decreases because a certain amount methanol is driven to the top of the
reactive distillation stages without converting to dimethyl ether. More-
over, the purity of the dimethyl ether decreases because it contains a
significant amount of unreacted methanol above the reactive stages.
The effects of reactive stages, rectifying stages and stripping stages
on the conversion of methanol are shown as Fig. 4(a)–(c). It can be seen
that the number of reactive stages is the most important parameter in
terms of the conversion of methanol, which rapidly increases as the
number of reactive stages is increased from 1 to 6. This is because
increasing the number of reactive stages results in an increase in the
mass transfer area and residence time of methanol to react in the
reactive stages. In addition, increasing the number of rectifying stages
Table 1
Standard conditions for the reactive distillation column for dimethyl ether produc-
tion.
Condition of feed
Temperature (K) 298
Crude glycerol feed flow rate (kmol h−1) 3.0786
Feed stage of crude glycerol 5
Column specification
Rectifying stages 3
Reaction stages 5
Stripping stages 3
Reboiler duty (kW) 50
Reflux ratio 1.2
Composition of crude glycerol feed (mol%)
Glycerol 70%
Methanol 30%
P. Kaewwisetkul et al. Chemical Engineering & Processing: Process Intensification 117 (2017) 80–88

Table 2
Standard conditions for the distillation column for purifying glycerol.

Condition of feed

Glycerol-water Temperature (K) 600

−1
Feed flow rate (kmol h )
Glycerol-water 2.62

Feed stage
Glycerol-water 5

Column specification
Total stages 11
Reboiler duty (kW) 6.02
Reflux ratio 1.9

Composition of glycerol-water feed (mol%)

Glycerol 82.3%
Water 17.7%

Fig. 2. Effect of reboiler duty on conversion of methanol.

Fig. 4. Effect of number of reactive stages (a), rectifying stages (b) and stripping stages (c)
on conversion of methanol.

Fig. 3. Effect of feed stages location on conversion of methanol. Fig. 6(a) shows that increasing the reboiler duty results in increasing
the purity of the glycerol in the glycerol stream by decreasing the
results in increasing the amount of methanol in the reactive stages. amount of water at the bottom of the distillation column. However, the
Moreover, the amount of dimethyl ether in the reactive stages slightly
decreases. This result enhances an increase in the conversion of
methanol. The effect of the number of stripping stages has a similar
trend as the rectifying stages as shown in Fig. 4(c). The conversion of
methanol can be increased by increasing the number of stripping stages.
This is due to the fact that increasing the number of stripping stages
results in an increasing amount of methanol in the reactive stages.
Fig. 5 shows the impact of the reflux ratio on conversion of
methanol. An increase in the reflux ratio results in more unreacted
methanol being fed back to the column. For this reason, the conversion
of methanol can be increased by increasing the reflux ratio.

4.2. Distillation for glycerol separation

The effects of operating parameters, such as reboiler duty, number

of stages and reflux ratio are shown in Fig. 6(a)–(c), respectively. Fig. 5. Effect of reflux ratio at varying numbers of reactive stages.

83
P. Kaewwisetkul et al. Chemical Engineering & Processing: Process Intensification 117 (2017) 80–88

Fig. 6. (a) Effect of reboiler on molar flow rate of glycerol and mole fraction of water in pure glycerol stream, (b) effect of number of stages on glycerol fraction in pure glycerol stream
and (c) effects of reflux ratio on molar flow rate of glycerol and mole fraction of water in pure glycerol stream.

molar flow rate of the glycerol stream decreases slightly at a reboiler
duty of more than 5 kW.
Fig. 6(b) demonstrates the effect of extending the number of stages
while the other operating parameters remain the same as standard
conditions. The results show that the number of stages is not significant
in terms of glycerol purity due to the difference in boiling point
between glycerol and water. The glycerol flow in the glycerol stream
is increased with increasing reflux ratio because the glycerol at the
condenser is returned to the distillation column as shown in Fig. 6(c).
However, water contamination in the glycerol stream is increased by
increasing the reflux ratio.
5. Economic assessment for the optimal design of reactive
distillation for dimethyl ether production and glycerol
purification
In this section, the reactive distillation for dimethyl ether produc-
tion is designed in term of economic criteria. The objective function is
the minimization of total annual cost. The constraints are 99%
conversion of methanol and 99% purity of dimethyl ether as shown
in the assumptions. The optimal design variables such as operating
pressure, the number of reactive stages, the number of rectifying stages,
the number of stripping stages and feed location are determined.

84
P. Kaewwisetkul et al.
5.1. Economic assessment for dimethyl ether production
The operating pressure of the reactive distillation column for
dimethyl ether production is not 1 bar because the temperature range
of the separation must correspond to the reaction temperature. For this
reason, the optimum pressure of reactive distillation for dimethyl ether
production is investigated by using the total annual cost as the
criterion. The standard conditions for reactive distillation are used in
this section. However, the number of reactive stages is increased to 7
reactive stages in order to increase the conversion of methanol to 99%.
The variables of reflux ratio and reboiler duty are manipulated until the
product specification is met. The total annual cost (TAC) is defined as
shown in Eq. (5).
TACcap
TAC=TACope+
Payback Period (5)
The tray sizing function in the Aspen Plus simulation was used to
estimate the diameter of the reactive distillation column. The distance
between trays is kept at 2 ft. The calculations of the capital cost
(TACcap) and operating cost (TACope) were performed following the
procedure in Douglas [18]. The annualized capital cost was calculated
with a payback period of 3 years and using the cost data from Appendix
B of Douglas [18].
5.1.1. Operating pressure
Assumptions and specifications for the dimethyl ether stream and
reactive distillation design are as follows:
1. The design objective is to obtain 99 mol% conversion of methanol
2. The purity of the dimethyl ether is 99 mol%
3. The number of rectifying stages, reactive stages and stripping stages
is fixed at 3, 7 and 3 respectively.
4. The feed location of crude glycerol is fixed at stage 5
The design procedure for finding the optimum pressure for reactive
distillation is shown in Fig. 7. From the simulation result, Fig. 8
indicates that an operating pressure of 9 bar for reactive distillation
provides the lowest total annual cost.
5.1.2. Number of stages
Assumptions and specifications for the design of reactive distillation
are as follows:
1. The design objective is to obtain 99 mol% conversion of methanol
2. The purity of dimethyl ether in the dimethyl ether stream is 99 mol
%
3. The flow of dimethyl ether in the dimethyl ether stream is
0.457 kmol h−1
4. Crude glycerol is fed at the first reactive stage.
5. The reactive distillation is operated at 9 bar.
Based on these assumptions and specifications, the design variables
are as follows:
1. Number of rectifying stages
2. Number of stripping stages
3. Number of reactive stages
The design procedure for the reactive distillation column is shown
in Fig. 9.
Fig. 10 shows the number of reactive stages is an important
parameter. Increasing the number of reactive stages leads to an increase
in mass transfer area and residence time for methanol to react in the
reactive stages. For this reason, the conversion of methanol also
increases. Secondly, increasing the number of reactive stages can
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Chemical Engineering & Processing: Process Intensification 117 (2017) 80–88
improve the separation of light product as dimethyl ether from the
water by-product and glycerol. Furthermore, it can reduce the energy
consumption and size of the reboiler. Thus increasing the number of
reactive stages can reduce both the operating cost and capital cost of
the reboiler. However, increasing the number of reactive stages to more
than 8 stages results in a higher capital cost. We concluded that the
optimum number is 8 reactive stages.
The effects of the reactive stages, rectifying stages and stripping
stages of the reactive distillation column are demonstrated in
Fig. 11(a)–(c), respectively. Because methanol is completely consumed
in the reactive stages, the only remaining components in the reactive
distillation column are dimethyl ether, glycerol and water. The boiling
points of glycerol and water are higher than that of dimethyl ether, so
the separation of dimethyl ether from water and glycerol requires a few
rectifying and stripping stages to achieve purity specification.
Increasing the number of rectifying stages can provide the separa-
tion of dimethyl ether from the reactive stages. This result reduces the
reboiler duty and condenser, so the operating cost can be reduced by
increasing rectifying stages. It is found that increasing the number of
stripping stages provides many benefits. Firstly, it offers a better
separation of methanol from the reactive stages. For these reasons,
the operating cost of the reboiler is reduced. Secondly, increasing the
number of stripping stages can provide high purity of glycerol at the
bottom of the reactive distillation column. However, increasing the
number of rectifying and stripping stages requires more capital cost.
The results show that the optimum number of rectifying stages is 2 and
the optimum number of stripping stages is also 2.
For the effect of the reflux ratio, increasing the reflux ratio leads to
recycling unreacted methanol back to the column. For this reason,
conversion of methanol can be increased by increasing reflux ratio.
However, a higher reflux ratio requires greater operating cost.
For the effects of the reboiler duty, increasing reboiler duty results
in increasing water in the reactive stages, which inhibits the dehydra-
tion of methanol. However, there is an opposite trend in the amount of
methanol in the reactive stages. For this reason, conversion of methanol
is decreased by increasing reboiler duty. However, reboiler duty must
operate at a sufficiently high value to separate dimethyl ether from the
glycerol and water. The optimal operating reboiler duty is 49.43 kW.
The optimal operating parameters of the reactive distillation column
are summarized in Table 3.
5.2. Economic assessment of the distillation column for production of pure
glycerol
This section studies the steady-state economics of the distillation
column for the separation of glycerol from water. An optimum
Fig. 7. Design procedure for finding optimum pressure of the reactive distillation column
for glycerol and ether production.
P. Kaewwisetkul et al. Chemical Engineering & Processing: Process Intensification 117 (2017) 80–88

Fig. 8. Relationship of the pressure in the reactive distillation column operation on total
annual cost.

Fig. 11. The effect of rectifying and stripping stage on total annual cost of reactive
Fig. 9. Design procedure of the reactive distillation column for dimethyl ether produc- distillation for dimethyl ether production by fix reactive stages at (a) 7 stages, (b) 8 stages
tion. and (c) 9 stages.

Table 3
Optimal operating parameters of the reactive distillation column for dimethyl ether
production.

Condition of feed

Temperature (K) 298

Crude glycerol feed flow rate (kmol h−1) 3.078
Crude glycerol Feed stage 5

Column specification
Rectifying stages 2
Reaction stages 8
Stripping stages 2
Reboiler duty (kW) 49.43
Reflux ratio 0.22
Fig. 10. Effects of reactive stages on total annual cost.
Composition of crude glycerol stream (mol%)
Glycerol 70%
distillation column for production of pure glycerol by using the total Methanol 30%
annual cost as the criterion is investigated. The total annual cost
includes the operating cost and annualized capital cost. The optimal

86
P. Kaewwisetkul et al.
Fig. 12. Design procedure for the distillation column for separation of glycerol from
water.
Fig. 13. Effects of feed location (a) and number of stages (b) on total annual cost.
operation parameters, including the number of stages, reflux ratio,
reboiler duty etc., are obtained by calculating a minimum total annual
cost.
Assumptions and specifications for glycerol stream are shown
below:
1. The purity of glycerol in the glycerol stream is 99.9 mol%
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Chemical Engineering & Processing: Process Intensification 117 (2017) 80–88
Table 4
Optimal operating parameters of the distillation column.
Condition of feed
Temperature (K) 599.64
Feed flow rate (kmol h−1) 2.62
Feed stage 5
Main composition of feed (mol%)
Glycerol 82.3%
Water 17.5%
Column specification
Total stages 11
Reboiler duty (kW) 6.021
Reflux ratio 1.92
2. The glycerol flow rate in the glycerol stream is 2.15 kmol h−1
Based on these assumptions and specifications, the design variables
are as follows:
1. Number of stages
2. Location of the feed stage
The design procedure for the distillation column for the separation
of glycerol from water is shown in Fig. 12.
For the distillation column, the reflux ratio is an important
parameter. The glycerol flow and water contamination in the glycerol
stream is increased by increasing the reflux ratio. The reflux ratio must
be operated at a sufficiently high value to maintain the glycerol flow
rate at 2.15 kmol h−1 in the glycerol stream. However, an excessive
reflux ratio results in decreasing purity of the glycerol in the glycerol
stream. For this reason, the reflux ratio must be operated at 1.92 in
order to maintain both the molar flow rate of glycerol and the
constraint on the purity of the glycerol in the glycerol stream. A higher
reflux ratio results in a higher total annual cost.
Increasing reboiler duty results in increasing the purity of the
glycerol in the pure glycerol stream. However, the molar flow rate of
the glycerol stream is slightly decreased at a reboiler duty of more than
5 kW. Moreover, a higher reboiler duty results in higher total annual
cost. Fig. 13(a) demonstrates the effects of the location of the feed stage
on the total annual cost. The feed stage must be at such a location in
order to have the appropriate number of stages below and above the
feed stage location. Fig. 13(b) demonstrates that 11 stages for the
distillation column gives the lowest total annual cost at both the same
purity of glycerol and glycerol flow rate in the pure glycerol stream.
Because the purity of the glycerol stream is increased as the number
of stages increases, the reboiler duty for separation of water from the
glycerol can be reduced. For this reason, operating cost is reduced.
However, increasing the number of stages requires a greater capital
cost. The optimal number of stages in the distillation column is 11.
The optimal operating parameters of distillation column are sum-
marized in Table 4.
6. Conclusions
Reactive distillation for the production of dimethyl ether by the
dehydration of methanol is investigated. Reactive distillation was used
to improve the performance of dimethyl ether production in terms of
the conversion of methanol. The RADFRAC module in Aspen Plus is
used to study the parameters of the reactive distillation column such as
reflux ratio, reboiler duty, and the number of stages on its performance
in terms of the conversion of methanol. The optimal configurations of
reactive distillation are also determined using a total annual cost. The
methanol in crude glycerol was completely consumed in the reactive
stage. Therefore, a recycle section for the recovery of methanol is not
essential. In conclusion, this approach can reduce the energy require-
P. Kaewwisetkul et al.
ment. For the effects of the parameters of the reactive distillation
column, increasing the number of reactive stages, the number of
rectifying stages, the number of stripping stages and the reflux ratio
results in increasing conversion of methanol. However, increasing the
reboiler duty gives an opposite trend but this parameter is important in
accomplishing the separation. The suitable feed stage location for the
crude glycerol in the reactive stages is the first reactive stage. For the
effects of the parameters of the distillation column, increasing the
number of stages and reboiler duty gives increases the purity of the
glycerol. Reflux ratio is also an important parameter in terms of the
molar flow rate of glycerol in the glycerol stream. However, water
contamination in glycerol is increasing by increasing the reflux ratio.
The optimal reactive distillation configurations for dimethyl ether
production using total annual cost consist of two rectifying stages,
eight reactive stages and two stripping stages. The optimal number of
stages of the distillation column for the production of pure glycerol is
11 stages.
Acknowledgments
Support from The Institutional Research Grant (The Thailand
Research Fund) (IRG 5780014) and Chulalongkorn University
(RES_57_411_21_076) is gratefully acknowledged. L. Simasatitkul
would like to thank Faculty of Applied Science, King Mongkut’s
University Technology of North Bangkok.
References
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